Facile Synthesis of Glycopolypeptides by Combination of Ring‐Opening Polymerization of an Alkyne‐Substituted N‐carboxyanhydride and Click “Glycosylation”

Abstract

Synthetic glycopolypeptides have attracted much interest for application in biomedical field as they are structural mimics to the natural glycopeptides or glycoproteins. However, the synthesis methods toward glycopolypeptides are still few or less efficient. Herein, we present a facile route to preparation of glycopolypeptides with highly effective "glycosylation" by click postpolymerization modification. First, an alkyne-substituted N-carboxyanhydride (NCA) monomer was synthesized and subsequently polymerized to afford the polypeptide with "clickable" alkyne pendants. The alkyne-functionalized polypeptide was then "glycosylated" by click reaction of different sugar azides to the alkyne pendants with high efficiency. All the obtained glycopolypeptides were soluble and preferred α-helix conformation in water. Primary studies on the obtained glycopolypeptides binding with Con A lectin were assessed by turbidimetric assay. The more quantitive studies of the interactions between lectin proteins and the synthetic glycopolypeptides, and the application of these materials as the multivalent ligands are in progress.

Facile Synthesis of Fluorescent Latex Nanoparticles with Selective Binding Properties Using Amphiphilic Glycosylated Polypeptide Surfactants

“…In all but one experiment high styrene conversion and stable particle dispersion were obtained. Only in the case of using a low concentration of PS 45 -b-(PLL 47 -r-LA 28 ) 75 (i.e., 2 pphm) a stable latex could not obtain, which implies that PS 45 All three curves show the absence of a nucleation period typical for a conventional ab initio emulsion polymerization. This behavior, which we observed before, suggests that the block copolymer micelles present at the start of the reaction act as a seed and are converted into particles.…”

“…DMT-MM allows for a high degree of substitution while it has been shown to be a very versatile component in preparing poly(glutamic acid) derivatives with orthogonal reactive sites. 59 For PS 45 -b-PLL 75 , EDC/ NHS coupling chemistry was used to attach lactobionic acid (LA, 4-O-β-galactopyranosyl-D-gluconic acid, 7) to the lysine residues typically targeting 35% glycosylation of the PLL block. LA is a readily available disaccharide with a galactose moiety and a cost-effective alternative to the functional sugars typically incorporated in other glycosylation strategies.…”

“…The emulsion polymerization of styrene stabilized by either PS 45 -b-(PLGA 31 -r-GA 35 ) 66 5 or PS 45 -b-(PLL 47 -r-LA 28 ) 75 6 was carried out in order to evaluate the ability of the hybrid conjugates to form stable polystyrene nanoparticles with a brushlike periphery. All reactions were performed using potassium persulfate as a water-soluble initiator at 70°C and a concentration of 1 wt % with respect to monomer (1 pphm).…”

“…PS 45 -b-(PLL 47 -r-LA 28 ) 75 (6). A general procedure for 1-ethyl-3-[3-(dimethylamino)propyl]carbodiimide hydrochloride (EDC)/N-hydroxysuccinimide (NHS) coupling was employed to attach lactobionic acid to the lysine residues of the amphiphile.…”

“…PS 45 -b-(PLL 45 -r-LA 26 -r-FITC 2 ). Fluorescein isothiocyanate (FITC) was attached to the lysine residues at 1.5 mol equiv per chain.…”